JP2500941B2 - Pigment composition and paint and printing ink using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a pigment composition and a paint or a printing ink which are excellent in suitability for use, particularly non-aggregation, non-crystallinity and fluidity.

(Prior Art) Highly halogenated copper phthalocyanine has a beautiful color tone,
Although it is a green pigment widely used for coloring materials due to its great tinting strength and various fastnesses, it still has unsatisfactory properties depending on the application.

Generally, the particle size of highly halogenated copper phthalocyanine is very small, and one of the major drawbacks due to this is the aggregation property. This tendency is remarkably observed in non-aqueous low-viscosity dispersions such as paints and gravure inks, but as a result of pigment aggregation,
It has a large structural viscosity in terms of fluidity and may cause practical problems such as color separation and pigment settling in a paint mixed with another type of pigment.

Several methods have been proposed to remedy this drawback. For example, a method of mixing a copper phthalocyanine derivative as shown in USP 3,891,455 with a highly halogenated copper phthalocyanine, a polysulfonic acid alkaline earth metal salt of a highly halogenated copper phthalocyanine as disclosed in JP-B-40-4143. Alternatively, a method of mixing a higher aliphatic amine salt with a highly halogenated copper phthalocyanine, etc. When these methods are additionally tested, the gravure ink system shows excellent gloss and low viscosity, but the effect on the paint system is small.

Further, as disclosed in JP-A No. 52-132031, a method of mixing a blue-colored copper phthalocyanine derivative with a highly halogenated copper phthalocyanine has been proposed. However, JP-A-52-132031, 47-10829, 47-10831, 48-41202, 51
-34235, 51-34236, 51-133323, etc., blue copper phthalocyanine derivatives as seen in each publication, etc. are mixed with highly halogenated copper phthalocyanine to prepare a paint or printing ink, etc. Although properties such as properties are improved, the hue becomes bluish, the green hue characteristic of the highly halogenated copper phthalocyanine pigment is impaired, and the value as a green pigment is lost.

Further, as a means for solving the problem relating to the hue of such a highly halogenated copper phthalocyanine, a green color represented by the formula (E) or the formula (F) in JP-A-59-168070 is used. A method of mixing a copper phthalocyanine derivative with a highly halogenated copper phthalocyanine has been proposed.

(The meaning of the symbols in the formula is the same as in formula (I) and formula (II)) However, these copper phthalocyanine derivatives are
There are many very disadvantageous or unreasonable points in their manufacturing process. For example, in the case of producing a copper phthalocyanine derivative represented by the formula (E), it is necessary to produce a copper phthalocyanine having a carboxyl group. However, copper phthalocyanine undergoes a substituent introduction reaction to introduce a carboxyl group. Since it is very difficult to do so, it must be carried out from the synthesis of the copper phthalocyanine skeleton using phthalic anhydride or phthalimide having a carboxyl group, which is very unreasonable industrially. Further, in order to produce the copper phthalocyanine derivative represented by the formula (F), it is necessary to introduce a chlorosulfone group into copper phthalocyanine to produce a copper phthalocyanine sulfonic acid chloride, but many chlorosulfone groups are introduced. It is difficult for the chlorosulfone group to be hydrolyzed, and the sulfone group produced by hydrolysis of the chlorosulfone group is likely to remain in the copper phthalocyanine derivative represented by the formula (F). May affect

Incidentally, the pigment dispersion performance of the copper phthalocyanine derivative is often greatly different due to the difference in its chemical structure, and it cannot be said that the copper phthalocyanine derivative having the above chemical structure is necessarily effective for dispersing the highly halogenated copper phthalocyanine pigment. .

(Means for Solving the Problems) The present invention provides a pigment composition comprising 100 parts by weight of a highly halogenated copper phthalocyanine and 0.1 to 30 parts by weight of a copper phthalocyanine derivative represented by the formula (I) or the formula (II), and The present invention relates to paints and printing inks comprising the pigment composition and a vehicle for paints or a vehicle for printing inks.

CuPc: represents a copper phthalocyanine residue.

X: represents a chlorine atom or a bromine atom.

A: represents —CH ₂ — or —CH ₂ NHCOCH ₂ —.

R ₁ and R ₂ : each independently represent an optionally substituted saturated or unsaturated alkyl group or R ₁ and R ₂ which may be substituted and have a nitrogen, oxygen or sulfur atom.

l: represents an integer of 4 to 15.

m: represents an integer of 1 to 20.

n: represents an integer of 1 to 10.

The highly halogenated copper phthalocyanine in the present invention refers to one having a chlorine and / or bromine substitution number of 8 to 16.

The copper phthalocyanine derivative represented by the formula (I) or (II) has a total number of chlorine and / or bromine substituents of 4 to 15, and when the number of substituents is 3 or less, the copper phthalocyanine derivative is a blue compound. When mixed with a highly halogenated copper phthalocyanine pigment, it causes a problem that the hue of the paint and the printing ink becomes bluish. On the other hand, when the total number of substituents of chlorine or bromine is 4 or more, the copper phthalocyanine derivative represented by the formula (I) or the formula (II) becomes a green compound,
Even when it is mixed with a highly halogenated copper phthalocyanine pigment and used, the green hue of the pigment is not impaired. The total number of chlorine and bromine substituents in the copper phthalocyanine derivative represented by formula (I) or formula (II) is practically advantageous in the range of 5 to 10.

Although there are several synthetic routes for producing the copper phthalocyanine derivative according to the present invention, an outline of a typical production method will be described below by taking the copper phthalocyanine derivative represented by the formula (III) as an example 1), 2 ), 3).

1) A compound represented by formula (IV) is produced by reacting tri (chloromethyl) copper phthalocyanine with diethylamine.

Next, the compound represented by the formula (IV) is chlorinated to produce a copper phthalocyanine derivative represented by the formula (III).

2) Chlorination of tri (chloromethyl) copper phthalocyanine produces a compound represented by the formula (V).

Formula (V) (Cl) ₆ -CuPcCH ₂ Cl) ₃ Then, the compound represented by Formula (V) is reacted with diethylamine to produce a copper phthalocyanine derivative represented by Formula (III).

3) Hexachlorocopper phthalocyanine is tri (chloromethyl) ated to produce a compound represented by the formula (V).
Next, the compound represented by the formula (V) is reacted with diethylamine to produce a copper phthalocyanine derivative represented by the formula (III).

In the formula (I) and the formula (II), A is —CH ₂ NCO.
CH ₂ −, that is, formula (VI) or formula (VI
When a chloroacetylaminomethylated copper phthalocyanine represented by I) is used as a reaction intermediate, the copper phthalocyanine derivative according to the present invention can be produced by the same method as in 1), 2) and 3) above. it can.

Formula _{(VI) CuPcCH 2 NHCOCH 2 Cl} ) n formula _{(VII) X l -CuPcCH 2 NHCOCH} 2 Cl) n (X, l, n also is as defined above), copper having a chloromethyl group or a chloroacetyl aminomethyl group In the reaction of phthalocyanines and amines, a basic compound such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, triethylamine, pyridine, p-dimethylaminopyridine or the like is used in combination as a dehydrochlorinating agent. You can also

In formula (I) or formula (II), Or Examples of the amines used to form the compound include dimethylamine, diethylamine, N-ethylisopropylamine, N-ethylpropylamine, N-methylbutylamine, N-methylisobutylamine, N-butylethylamine, N-tert. -Butylethylamine, diisopropylamine, dipropylamine, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di ( 2-ethylhexyl) amine, dioctylamine, N-methyloctadecylamine, didecylamine, diallylamine, N-ethyl-1,2-dimethylpropylamine, N-methylhexylamine, 2-hydroxymethylaminoethano , Dioleoylamine,
Distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N -Diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N
-Butylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N
-Diisobutylaminopentylamine, N, N-methyl-
Laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-diester aminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline , 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid,
Methyl isonicopetate, ethyl isonicopetate, 2
-Piperidine ethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopyropyrpiperidine, N-aminopropyl-2-pipecoline, N- Aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine and the like.

The amount of the copper phthalocyanine derivative represented by the formula (I) or the formula (II) is 0.1 to 100 parts by weight of the highly halogenated phthalocyanine.
-30 parts by weight are preferred. When less than 0.1 parts by weight, the effect of the copper phthalocyanine derivative according to the present invention cannot be obtained,
Even if more than 30 parts by weight is used, the effect of the amount used cannot be obtained.

Examples of the method of using the highly halogenated copper phthalocyanine and the copper phthalocyanine derivative represented by the formula (I) or the formula (II) include the following methods.

1. A pigment composition obtained by previously mixing a highly halogenated copper phthalocyanine and a copper phthalocyanine derivative is added to a non-aqueous vehicle or the like and dispersed.

2. Separately add highly halogenated copper phthalocyanine and copper phthalocyanine derivative to a non-aqueous vehicle and disperse.

3. Highly halogenated copper phthalocyanine and copper phthalocyanine derivative are separately dispersed in a non-aqueous vehicle or the like in advance, and the resulting dispersion is mixed.

In this case, the copper phthalocyanine derivative may be dispersed only with the solvent.

4. After dispersing highly halogenated copper phthalocyanine in a non-aqueous vehicle or the like, a copper phthalocyanine derivative is added to the obtained dispersion.

The desired effects can be obtained by any of these methods.

As a method for preparing the pigment composition shown in the above 1, the desired effect can be obtained by simply mixing the highly halogenated copper phthalocyanine pigment powder and the powder of the copper phthalocyanine derivative according to the present invention. , Mechanically mixed with an attritor, a super mill, various pulverizers or the like, or a solution containing the copper phthalocyanine derivative according to the present invention is added to a suspension system of highly halogenated copper phthalocyanine pigment with water or an organic solvent, and the pigment surface is added. Intimate mixing method such as depositing copper phthalocyanine derivative on the above or co-dissolving highly halogenated copper phthalocyanine and copper phthalocyanine derivative in a solvent having strong dissolving power such as sulfuric acid and coprecipitating with a poor solvent such as water. Then, a better result can be obtained.

Further, in the use of the highly halogenated copper phthalocyanine and the copper phthalocyanine derivative shown in the above 2 to 4,
Dispersion of highly halogenated copper phthalocyanine or copper phthalocyanine derivative in a non-aqueous vehicle or solvent, use of a dissolver, high speed mixer, homomixer, kneader, roll mill, sand mill, attritor, etc. as a dispersing machine for mixing these As a result, the highly halogenated copper phthalocyanine can be dispersed well.

In the present invention, a paint and a printing ink are included as an application of the pigment dispersion.

In the paint, the pigment composition of the present invention is 0.1 to 15% by weight, the paint dissolution vehicle is 99.9 to 55% by weight, other auxiliary agents and extender pigments 0
-30% by weight, the vehicle for paint is acrylic resin,
Alkyd resin, epoxy resin, chlorinated rubber, vinyl chloride,
Synthetic resin emulsion, silicone resin, water-soluble resin,
It comprises 80 to 20% by weight of polyurethane, polyester, melamine resin and urea resin or a mixture thereof and 60 to 10% by weight of solvent such as hydrocarbon, alcohol, ketone, ether alcohol, ether, ester and water.

The gravure ink comprises 3 to 20% by weight of the pigment composition of the present invention, 97 to 60% by weight of a vehicle for gravure ink, and 0 to 20% by weight of other auxiliary agents and extender pigments. The vehicle for gravure ink includes gum rosin, wood rosin, Tall oil rosin, lime rosin, rosin ester, maleic acid resin, polyamide resin, vinyl resin, nitrocellulose,
Resin mixture such as cellulose acetate, ethyl cellulose, ethylene-vinyl acetate copolymer resin, urea resin, polyester resin, alkyd resin, gilsonite, dammar, shellac 10 to 50% by weight, hydrocarbon, alcohol, ketone, ether alcohol, ether, ester , 30 to 80% by weight of a solvent such as water.

The offset ink comprises 3 to 35% by weight of the pigment composition of the present invention, 97 to 45% by weight of the vehicle for offset ink, and 0 to 20% by weight of other auxiliary agents and extender pigments. The vehicle for offset ink is a rosin-modified phenol resin, 20 to 50% by weight of resin such as petroleum resin, alkyd resin or dry oil modified resin, 0 to 30% by weight of vegetable oil such as linseed oil, tung oil, soybean oil, n-paraffin, isoparaffin, aromatech, naphthene, It is composed of 10 to 60% by weight of a solvent such as α-olefin.

(Effects of the Invention) According to the present invention, compared with the case where a highly halogenated copper phthalocyanine pigment is used alone, it exhibits good fluidity such as a decrease in viscosity of the dispersion and a decrease in structural viscosity, and at the same time, color separation and crystal formation The gloss of the printed matter or the coating film is good without any problems such as change and hue change, and thus a beautiful product can be obtained.

In particular, the pigment composition according to the present invention has an extremely excellent dispersing effect not only in oil-modified aminoalkyd resin paints but also in oil-free alkyd resin paints.

Further, the use of the pigment composition according to the present invention is not limited to only non-aqueous vehicles, other printing inks and paints,
Further, also in coloring of plastics, it is possible to obtain a colored product having an excellent dispersing effect and coloring power.

The production examples of the copper phthalocyanine derivative represented by the formula (I) or the formula (II) are shown below. The following "parts"
Means "parts by weight", and the numbers of the copper phthalocyanine derivatives in Production Examples are the same as the abbreviations of the copper phthalocyanine derivatives shown in Table 1.

[Production Example 1] 200 parts of aluminum chloride and 40 parts of sodium chloride were heated to form a eutectic salt at 170 ° C, 46 parts of bis (chloromethyl) copper phthalocyanine was charged, and chlorine gas was supplied at a rate of 4 parts per hour for 8 hours. Introduced. After completion of the reaction, the mixture was poured into a large amount of water, the precipitate was washed with water, and then dispersed again in 800 parts of water.
Then, 22 parts of diethylamine was added, the temperature was raised to 80 ° C., and the mixture was stirred at the same temperature for 5 hours. The product was filtered, washed with water and dried to obtain 55 parts of copper phthalocyanine derivative (1).

[Production Example 2] 40 parts of chloroacetylaminomethylcopper phthalocyanine was dispersed in 800 parts of water, 23 parts of N, N-dimethylaminopropylamine was added, and the temperature was raised to 90 ° C. The mixture was stirred at the same temperature for 10 hours, and the precipitate was washed with water, dried, and pulverized. This product was added to a mixed solution of 800 parts of titanium tetrachloride and 37 parts of aluminum chloride, the temperature was raised to 135 ° C., and chlorine gas was introduced at a rate of 5 parts per hour for 24 hours. After completion of the reaction, pour into a large amount of water,
After washing, washing with water and drying, copper phthalocyanine derivative (2) 81
Got a part.

[Production Example 3] 20 parts of tris (chloromethyl) copper phthalocyanine was added to 400 parts of dibutylamine, heated to 100 ° C., and stirred at the same temperature for 6 hours. This reaction liquid was poured into 1500 parts of water, and the obtained precipitate was filtered, washed with water, dried and pulverized. This product, 100 parts of aluminum chloride and 25 parts of sodium chloride,
The mixture was charged in a eutectic salt containing 0.4 part of iodine at 150 ° C., and bromine was added at a rate of 6 parts per hour for 10 hours. After the reaction was completed, it was poured into a large amount of water, filtered, washed with water and dried to obtain 45 parts of a copper phthalocyanine derivative (3).

[Production Example 4] After 200 parts of aluminum chloride and 40 parts of sodium chloride were heated to form a eutectic salt at 200 ° C, 40 parts of bis (chloroacetylaminomethyl) copper phthalocyanine was added and cooled to 170 ° C to remove bromine. After introducing at a rate of 2 parts per hour for 60 hours, chlorine gas was introduced at a rate of 4 parts per hour for 8 hours. After completion of the reaction, the mixture was poured into a large amount of water, the precipitate was washed with water, and then dispersed again in 800 parts of water. Next, 38 parts of N-methylpiperazine was added, the temperature was raised to 85 ° C., and the mixture was stirred at the same temperature for 9 hours. The product was filtered, washed with water and dried to obtain 78 parts of a copper phthalocyanine derivative (4).

Table 1 shows some structural examples of the copper phthalocyanine derivative according to the present invention.

In order to evaluate the performance of the pigment composition according to the present invention,
A paint and a gravure ink having the following composition were prepared.

Formulation (1) Highly halogenated copper phthalocyanine pigment 9.5 parts Copper phthalocyanine derivative 0.5 parts Alkyd resin varnish (nonvolatile content 60%) 26.4 parts Melamine resin varnish (nonvolatile content 50%) 13.6 parts Thinner (xylene / n-butanol = 8/2) 20 parts Mixed varnish added after dispersion (alkyd / melamine = 7/3 (solid content)) 48.3 parts Formulation (2) Highly halogenated copper phthalocyanine pigment 9.5 parts Copper phthalocyanine derivative 0.5 parts Oil-free polyester resin type 26.4 parts Varnish (nonvolatile content 60%) Melamine resin type varnish (volatile content 50%) 13.6 parts Swazol 20 parts Mixed varnish added after dispersion (alkyd / melamine = 7/3 (solid content) )) 48.3 parts Compounding (3) Highly halogenated copper phthalocyanine pigment 9.5 parts Copper phthalocyanine derivative 0.5 parts Polyamide / nitrocellulose varnish 70 parts Thinner 20 parts Add the above composition into a container and add a steel ball to a paint shaker. And dispersed to prepare a paint. These paints were compared with a paint to which no copper phthalocyanine derivative was added (a paint or a gravure ink containing 10 parts of a highly halogenated copper phthalocyanine pigment in the above composition without adding a copper phthalocyanine derivative) according to the following evaluation method.

Evaluation Method (1) Fluidity Evaluation Method The viscosity of the obtained pigment dispersion was 6 using a B-type viscometer.
It was measured at 60 rpm.

Evaluation method (2) Gloss evaluation method Oil paint was adjusted with a thinner for 23 seconds with a Ford cup 4, sprayed on an tin plate with an air spray gun, and then a baked paint plate was made. A gravure ink was triacetate film with a bar coater. The color was spread on and the glossiness was measured at 60 degrees with a gloss meter.

[Comparative Examples 1 to 6 and Examples 1 to 6] As is clear from Table 2, the pigment composition according to the present invention exhibited good dispersibility in all cases.

Even when the viscosity of these paints was measured with the same viscometer after being left for 1 week, almost no increase in viscosity was observed.
Also, make a 1/10 cut light color paint with white paint adjusted with titanium white, adjust the viscosity to 23 seconds with Ford cup 4,
The sample was taken in a test tube and the aggregated state was observed, but no color separation or sedimentation was observed even after one month.

In addition, the gravure ink showed good results as in the case of the paint.

Further, the pigment composition according to the present invention showed good dispersibility without agglomeration even in nitrocellulose lacquer, acrylic resin paint, water-soluble resin paint and the like.

Claims (3)

(57) [Claims] 1. A pigment composition comprising 100 parts by weight of a highly halogenated copper phthalocyanine and 0.1 to 30 parts by weight of a copper phthalocyanine derivative represented by the following general formula (I) or (II). CuPc: represents a copper phthalocyanine residue. X: represents a chlorine atom or a bromine atom. A: represents —CH ₂ — or —CH ₂ NHCOCH ₂ —. R ₁ and R ₂ : each independently represent an optionally substituted saturated or unsaturated alkyl group or R ₁ and R ₂ which may be substituted and have a nitrogen, oxygen or sulfur atom. l: represents an integer of 4 to 15. m: represents an integer of 1 to 20. n: represents an integer of 1 to 10. 2. A paint comprising the pigment composition according to claim 1 and a vehicle for paint. 3. A printing ink comprising the pigment composition according to claim 1 and a vehicle for a printing ink.